Lubricating oil manufacture



May 22, 1951 A. VOORHIES, JR

LUBRICATING OIL MANUFACTURE Filed Sept. 12, 1946 2 m 9 4 5 2 z a w 6 6 f,M V 6 d N z 8 Z i a we 2 av w MP0 llll' Patented May 22, 1951 2,554,282LUBRIGATING on. MANUFACTURE Alexis Voorhies, Jr.,

Baton Rouge, La., assignor to Standard Oil Development Company, acorporation of Delaware Application September 12, 1946, Serial No.696,604

3 Claims.

My invention relates to improvements in the manufacture of lubricatingoils and in particular it relates to correcting or improving theviscosity index of a lubricating oil and at the same time obtainingmaximum yields.

Heretofore and prior to my present invention lubricating oils have beensubjected to treatment with phenol for the purpose of dissolving out ofthe lubricating oil constituents which are detrimental thereto. Forexample, the ordinary crude lubricating oil stock contains aromaticcompounds which render the lubricating oil sensitive to temperaturechange, that is to say, heating the oil causes it to lower inordinatelyin viscosity. Of course, this is highly undesirable because, forexample, when the oil is to be used to lubricate an automobile engine,the high temperatures to which it is subjected on the bearings willcause the oil to become lower in viscosity to the extent that the oilfilm will be disrupted and to be of insufficient strength to preventwear. By treating the oil with a phenolic body the oil becomes lesssensitive to temperature increase. However, the treatment of alubricating oil stock with phenol often results in rather poor yieldsespecially if a high degree of improvement is sought, since the phenoltreating process merely separates good molecules from bad moleculeswithout efiecting any chemical change. In other words the phenoltreating process cannot create any new molecules of improvedcharacteristics.

I am aware that also prior to my present invention others have subjectedlubricating oil stocks to hydrogenation in the presence of catalysts forthe purpose of rendering the oil less sensitive to viscosity changeduring an increase in temperature. Improvement of lubricating oils byhydrogenation is a radically different process than phenol treating.Hydrogenation is essentially a chemical process; phenol extraction, aphysical process. With hydrogenation, the inferior molecules can beactually upgraded in quality; so that there exists the potentialities,with a superior catalyst, of achieving higher yields at a givenlubricating oil quality than obtainable by phenol extraction. The bestcatalyst heretofore used for improving a lubricating oil byhydrogenation is molybdenum sulfide. I,

have now discovered a new class of catalysts which improves thelubricating oil so as to render it less sensitive to a lowering inviscosity as the temperature increases, and at the same time, gives ahigher yield of desired product. Stated briefly at first, my catalystsare mixtures of metallic sulfides, that is to say, mixtures of sulfidesof metals of the sixth and eighth group of the periodic system such asfor example amixture. of nickel sulfide and tungsten sulfide.

The main object of my present invention therefore is to improve theproperty of a lubricating oil with respect to its viscosity index or itstend- Lubricating Oil Work-upz ency to decrease rapidly in viscosity asthe temperature of the oil increases.

In the accompanying drawing, 1 have shown diagrammatically an apparatuslayout in which a modification of my invention may be carried intoeffect.

In the drawing, l represents a reaction zone containing a body ofcatalyst. The oil to be treated enters the system through line 3 and ispumped by a pump 4 through a preheater 5 and then discharged into thebottom of I. Meanwhile, a hydrogen-containing gas enters the systemthrough line It], is pumped by pump ll into line 3 where it mixes withthe oil and passes with the latter through the preheater into thereaction zone I. Under conditions which will be subsequently describedby way of several specific examples, the desired conversion takes placein I, product is withdrawn through line [3, passed through a cooler l4and then separated in a separator I5. From separator l5 unconsumedhydrogen is separated and withdrawn through line 20 and pumped by pump2| into line 3 for furtheruse in the process. The oil is withdrawn fromseparator l5 through line '25 and then discharged into a frac-' tionaldistillation column 26 where it is separated into four fractions, asfollows:

(1) A gas which is withdrawn through line 21,

(2) A naphtha-gas oil fraction, which is withdrawn through line 28,

(3) A light lubricating oil, which is withdrawn through line 29, and

(4) The main product, which is withdrawn through line 36.

Example 1 Catalyst Pressure, pounds per sq. in. gauge H Gas Rate, Cubicfeet per barrel Feed.

Feed Rate, Volumes Feed per Volume Catalyst per hour Yield on Feed, Percent by Volume. Gravity, API Viscosity at F. (Seconds Saybolt Universal)Viscosity at 210 F. (Seconds Saybolt Universal) Viscosity Index 1 Pour,F Flash, F

A. S. T. M.D507-41 vide Ind. and Eng. Chem, vol. 32, pp. 102 107, 1940.

l A. S. T. M.D50T4l vide Ind. and Eng. Chem., vol. 32, pp. 102- 107,1940.

Example 3 Catalyst MoSz ZNiS-WS:

Pressure, pounds per sq. in. gauge 2, 500 Hi Gas Rate, Cubicieet perbarrel Feed 10, 000 Feed Rate, Volume Feed per Volume 2-) Catalyst perHour 0.6 Max. Temperature, F 720 750 Feed Product Lubricating OilWork-up:

Yield on Feed, Per cent by Volume. 100 77 Gravity, API 26.0 34. 4 33.0no Viscosity at 100 F. (Seconds Saybolt Universal) 520 225 230 Viscosityat 210 F. (Seconds Saybolt Universal) 04. 3 50. 9 51.1 Viscosity Index96 125 123 Pour, "F 120 115 120 Flash, F 480 475 450 3 a LA. S. T.M.D50741 vide Ind. and Eng. Chem., Vol.32, pp. 102- 107, 1,940.

Example 4 Catalyst MOS; ZNiS-WS:

Pressure, pounds per sq. in. gauge z, 500 H Gas Rate, Cubic feetpcrbarrcl Feed. 10, 000 Feed Rate, Volume Feed per Volume Catalyst perHour 0.6 Max. Temperature, F 750 775 Product Lubricating Oil Work'up:

Yield on Feed, Per cent by Volume. 100 48 Gravity, API 26. 0 36. 1 36. OViscosity at 100 F. (Seconds Say:

bolt Universal) 520 168 15 9 Viscosity at 210 F. (Seconds SayboltUnivcrsal) G4. 3 47. 0 46. 4 Viscosity Index 133 135 Four, F 120 110 95Flash, "F 480 440 400 1 A. S. T. M.D50741 vide Ind. and Eng. Ohcin,Vol.32, pp. 102- 107,1940.

It can be seen from the foregoing specific examples that for the samequality of lubricating oil I am enabled by my process employing mycatalysts to obtain a much higher yield of desired product. For example,in Example 1 the yield is increased from 48 volume per cent to 63 volumeper cent for the same quality oil. In other words, a yield increase ofnearly one third. Obviously this is very important from the standpointof economics. It is not intended herein to limit the catalystcomposition to the single formula shown above, but rather to embrace therange of mixed sulfide catalysts commonly employed for effectingsaturation of aromatic rings without concomitant excessive destructivehydrogenation. For example I may employ various mixtures of NiS and WS2,such as 0.5 to 50 mols of N18 per mol of W32. Also I may use 0.5 to 50mols NiS per' mol MOSz. Similarly other mixtures may involve 0.5 to 50mols A per mol B in the compound AS-BSz where A is an element of theeighth group of the periodic system and B an element of; the sixthgroup. Such mixed sulfides have. been employed in the past for selectivesimple hydrogenation of comparatively low boiling hydrocarbons, but sofar as I am aware have not been employed for lubricating oilimprovement.

Numerous modifications of my invention may made by those who arefamiliar with this art without departing from the spirit thereof.

ha I c aim is:

1. The method of upgrading a lubricating oil stock whichconsistsessentially in subjecting said stock to: the influence ofhydrogen and mild hydrogenation conditions of temperature and pressure,the presence-of a catalyst which consists essentially of a mixture oftwo mols of nickel sulfide; and one molof tungsten sulfide for asuflicient period of time to efiect the conversion of a major portion ofsaid stock to a lubricating oil of improved viscosity index andthereafter recovering said-v improved lubricating oil.

2. The method of upgrading a lubricating oil stock which consistsessentially in subjecting said stock; to. the influence of hydrogen andmild hydrogenation conditions including temperatures of, about TOW-750F. in the presence of a catalyst consisting of a mixture of nickelsulfid and tungsten sulfide in the approximate molar ratio of 2:1- for asufficient period of time to. efiect thecqnversion of a major portion ofsaid stock to.- a lubricating oil of improved viscosity index and;thereafter recovering; said improved lubrie t ng; Oi

3. The; method ofclaim 2 in which said conditionsinclude pressures ofabout 2590 lbs. per 59;. in, anda lubricating oil stock feed rate ofabout 0.2-0.6 volumes of feed per volume of catalyst, per hour.

ALEXIS VOORI-IIEKS, JR.

REFERENCES CITED The following. references are of record in the file.of; this. patent:

UNITED STATES PATENTS Number Name Date 1,908,286 Dorrer May 9, 19331,932,186. Pier et al. Oct. 24, 1933 1,932,369, Guthke Oct. 24, 19331,954,972. Yotmg Apr. 17, 1934 1,963,385 Russell June 19, 19342,278,407. Anthes et al Apr. 7, 1942 2,406,200 Cole Aug. 20, 19462,409,382 Peck Oct. 15, 1946 FOREIGN PATENTS Number Country Date 333,511Great Britain Aug. 5, 1930 48846.51. Great Britain July 7, 1938 OTHER.REFERENCES Ellis,- Hydrogenation of' Organic Substances,

3rdedi-tion; 1930; D. VanNostrand' Co., New York, pages 57 6-580".

-Hydrogenation of Petroleum by Haslam. et'

al., Ind: & Eng Chem. vol. 22; No. 10; pages 1030 to 1034, Oct, 1930.

1. THE METHOD OF UPGRADING A LUBRICATING OIL STOCK WHICH CONSISTSESSENTIALLY IN SUBJECTING SAID STOCK TO THE INFLUENCE OF HYDROGEN ANDMILD HYDROGENATION CONDITIONS OF TEMPERATURE AND PRESSURE IN THEPRESENCE OF A CATALYST WHICH CONSISTS ESSENTIALY OF A MIXTURE OF TWOMOLS OF NICKEL SULFIDE AND ONE MOL OF TUNGSTEN SULFIDE FOR A SUFFICIENTPERIOD OF TIME OF EFFECT THE CONVERSION OF A MAJOR PORTION OF SAID STOCKTO A LUBRICATING OIL OF IMPROVED VISCOSITY INDEX AND THEREAFTERRECOVERING SAID IMPROVED LUBRICATING OIL.